Secondary self-assembly behaviors of PEO-b-PtBA-b-PS triblock terpolymers in solution

Abstract

A series of PEO45-b-PtBA53-b-PS x (x = 42, 84, 165) triblock terpolymers were synthesized by the atom transfer radical polymerization and characterized by size exclusion chromatography and 1H NMR. Their self-assemblies were conducted by a two-step hierarchical self-assembly method and a one-step dialysis method and the self-assembly behaviors were investigated. The morphologies, sizes, and size distributions of micelles produced by the self-assembly were determined by transmission electron microscopy and dynamic light scattering. The secondary self-assembled structure of PEO45-b-PtBA53-b-PS x obtained by the two-step hierarchical self-assembly could be controlled by tuning the length of PS block, the core forming block. The micelles were uniform with diameters of 20–25 nm and their size distributions, except for that of PEO45-b-PtBA53-b-PS165, were narrow with particle size distribution indexes ranging from 0.014 to 0.246. The one-step dialysis of the triblock terpolymers produced vesicular micelles with distinct vesicle walls that exhibited similar thicknesses. The vesicles did not show significant aggregation. The size distribution of PEO45-b-PtBA53-b-PS42 vesicle was the narrowest with a particle size distribution index value of 0.135. The PEO45-b-PtBA53-b-PS165 vesicles tended to overlap with each other.